Process of making hydrohalogenic acid.



Uwrirnn STATES 1 ratentect m 30, 1905;

PATENT OFFI E.

I GERMANY.

Paooeiss OF mamas HYDROHALOGENIC ACi D.

' SPECIFICATION forming part of Letters Patent No. 791,306, dated may :50, 1905.

I I I. application filed September 24,190 i. Serial No. 225,866.

To LIZ roll/077w it; Jim/y concern/a Be it known that I, F LIX VVILHEIM iffns r- HAUSSER, a subject of the King of Saxony, and

a resident or l-Iohenheim, near Stuttgart, Germany, haveinvented a Process for the Manufacture of Ilydr'ohaloge'nic Acid, of which the following is a specification.

The present invention relates to a process for theproduction of hydrohalogenicacid, and, more especially of hydrochloric acid and of hydrobromic acid.

It is well known thathydrochloric acid can becontinuously produced from chlorin and 7 hydrogen ifthese two gases in molecular quantities are brought into action directly on a contaet substance, such as carbon or platinum. Such a process, as has been proved to be the case, possesses certain drawbacks. Th us neither sufiicient yields can be obtained nor can explosions be avoided with certainty even when a certain excess of, hydrogen is v employed.

The new processv is based, on the one hand,

on the observation that a mechanical (1.,

chemically uncombined) mixture of chlorin andhydrogen is taken up by basic chloride or Oxy-chlorids and hydroxids'under conditidns stated below, a chlorid and, water being formed, and,on the otherhand, on the fact in itself well known that various 'chlorids of mctals--asfior-example in particular, aluminium chlorid,.zinc chlorid, and chlorid of tinif they are heated in the'presence of Water are decomposed partially into basic chloride or hydroxide (on the heating being continued, into oxide) and hydrochloric acid. The additional observation is of importance, that the basic chlorids or hydroxide hereby formed can be. always practically utilized again for the operationjof the taking 'up of chlorin and :hydrogen, with the formation of a chlorid and water. The reactionsin the case of the use of zinc compounds, for example, proceed according to the following equations:

1. ZnO1(OH)+Gl+H': snow-Hi0. 2. ZnCl2+H2O=ZnCl(OH)+HCl.

ZnGKOHH-l-hO ZniOHhi-HGL acid reaction which can be recognized by means of litmus, a phenomenon which indi- 'cates that a decomposition into basic chlorid occurred.

' The instauced reactions can be usefully employed in various ways according to the pres ent invention for the conversion of chlorin and hydrogen into hydrochloric acid. Thus the'mixture of chlorin and hydrogen produced, preferably,'by the electrolysis of solutions of common salt, potassium-'chlorid, and similar chlorids after being saturated can be either, first, conducted over porous rids to be decomposed or which are impregtions, or, second, allowed to act on the chlorid'solutious,the gases flowing in the oppositefidirection to the liquids as they trickle the aqueous solutions of the metal chloride, which can be effectedunder pressure or by 'means of a partial vacuum for example, by

spaces.

and a transitory fresh formation of chic by means of the operating gas mixture,

i For carrying out the process in agreei gut or hydroxid and hydrochloric acidhas already mated with their concentrated aqueous soludownward, or, third, allowed to flow through sucking oil' the gases from the electrode- The'action is based in all cases upon an alternating decomposition of the 'chlorid which is present or formed by means of heat;

'with water-vapor at a suitable temperature bodieswhich are charged with the metal chlo v with the above statements those chloride are suitable the solutions of which have an acid reaction with litmus, so that besides thechloride already mentionedv-iz., the chloride of I sjalumimuzn, zinc, and tinthse'of magneslum, sntimonymadrnimn, bismuth, and boron,

' "endslsdthcse of iron, chromium, and manganese, or mixtures of those chloride are also suitable, The temperature-to be observed is different for the 'difiehient chloride, and the degree otdecornposition also depends on the temperature employed. lln general temperatures of about 100 centigredegive good re sults;. but in the case of some chloride 2. higher temperature should be employed, and in the case of chlorid of tin, for example, the temperature should be even lower. Further, in the case of solutions being employed throughthe suliicient supply of water-vapor a water and wither thermometer and gas supply and delivery tube, are pieced one hun dred and fifty cubic centimeters of en alumini urn-chlorid solution of 1.233 to 1.35 specific gravity, which contains about twenty-six per cent. chlorin. Such-a solution begins at 110 centig'rede to give oil water and at about 120 centigrcde end forthwith if the heating is ceutiously continued precipitations are formed therein. In e second still-head hsv ing a capacity of about two hund red and fifty cubic eentimeters, which is provided with e gas-delivery tube and with a tube drawn out below so a capillary. tube for enebling sir to be sucked through and with two electrodes (for example, carbon electrodes} and which is connected with. the first stilhheed by means of s bottle containing water, which bottle is suitably warmed, two hundred cubic centimeters hydrochloric acid (1.1} are placed for this experiment. F rthwith electrolysis is proceeded with, a current of 1.5 smperes and a voltage of about four volts being; employed.

, The aluminium-chlorid solution in the first stilhhead is heated, for example, ins. sendhath to 120 M1130 centigrude, and the gas mixture evolved 1s sucked in a slow stream through the apparatus, warm water first of ,9 tenses all and then hot water being allowed to flow 6 into the eluminium-chlorid solution according as it distills oil. If after two hours the reaction is interrupted and air is sucked through the first still-head for the sake of removing the free chlorin which has resulted from the decomposition, the liquid being cooled there remains in the distillate collected in the receiver (from which distillate dissolved chlorin is previously likewise removed by sucking through air or by heating) 2.5 grams chlo- 7o rin, equal to 2.6 grams hydrochloric acid. If one reckons that in one hour 1.3X1'.5=2.0 grams chlorin end the equivalent quantity of hydrogen are evolved, it follows that 1.3

grams, equal to sixty-five per cent, are converted into hydrochloric acid. The chlorin left over can be employed in any desired manner. For example, it can be worked up into chlorid of lime. Also chlorinleft over can be 'reduced to a minimum by a suitable diminu- 8o tion of the intensity of the current. The aluminium-chlorid solution containing initially twenty-six percent. chlorin indicates in this experiment after the end of the reaction only 25.4 per cent. chlorin, which can bev explained by the is c: that the difference of 0.6 per cent. has been splitoif .orremoved as hydrochloric acid during the passage -ofthe@ The determination of the hydrochloric scid'wus urndcrtaken after being suitably diluted, accord 9o ing to Volhards method, by means of a onelifth normal silver-nitrate solution and ammonium sulfocyanid.

in the case oi the stated experiment, for the sake of more easily demonstrating the action of the process, the working mixture of the chlorin and hydrogen is produced by means of electrolysis from hydrochloric acid. For the practical process of the manufacture of hydrochloric acid according to the present I00 invention mixtures of chlorin and hydrogen are employed es oficred in practice. Thus. as already indicated above, hydrogen chlorin mixtures are employed whichlire obtained in the practical electrolysis of chlorid solutions. 1 5

These mixtures are then, like the hydrogenchlorin mixture obtdined for the above experiment by the electrolysis of hydrochloric acid, subjectedto the described action of one of the characterized chlorid solutions, technical carrying out of the process in rectice is, moreover, eilected in the same manner as ststcd in the case of the above-described cxperimcnt. It is only necessary to increase the quantities and the apparatus to a suitable ex- 1 l5 tent--for example, to lhcrease them tenfold or up to one hundred fold.

in an analogous manner hydrobromlc acid The no can also be manufactured according to the tially as described.

2. Process for the production of a. hydrohalogenic acid, consisting in 00116 noting; a me chanicel mixture'of its components in a humid condition and under the influence of heat over porons'bodies charged with decomposeole corresponding hnlogenicies of metals, substentiellyes described.

3; Process for the production of hydro chloric acid, consisting'in bringing a mechanical mixture of its components in a hn inicl condition end under the influence of heat 1 into reciprocal action with decomposable chlorids of metals, substantially as described. '4. Process for the production of hydrochloric acid, consisting in bringing a mechanical mixtureof its components in a humid condition and under the influence of heat into reciprocal action with aluminium chloriki,

substantially as described.

In testimony whereof I have signed my name tothis specification in the presence of two subscribing witnesses.

FELIX WILHELM WESTHAUSSER.

Witnesses:

' J OHN' OSWALD,

ERNST ENTERMANN; 

